The present invention relates to microelectronic trenched feature formation and more particularly to the formation of an interconnect from metal nanocrystal seeds.
An integrated circuit requires conductive interconnects between semiconducting domains in order to communicate signals therebetween. In order to create ever faster microprocessors, smaller dimension interconnects of higher conductivity materials is an ongoing goal.
As microelectronic efficiencies have increased, interconnects have decreased in dimensional size and efforts have been made to increase the electrical conductivity of interconnect features. There is an ongoing need for ever smaller interconnects.
The rapid miniaturization of interconnects is occurring simultaneously with the transition from Al to Cu metallization for sub-0.25 xcexcm ICs. The transition from Al to Cu has led to a change in the way interconnects are formed. While Al has been deposited as a blanket layer which is then patterned by reactive ion etching, Cu interconnects are formed by evaporative deposition into preformed (damascene) trenches and vias followed by chemical mechanical polishing (CMP).
As the interconnect width decreases and the aspect ratio increases, conventional vacuum deposition techniques approach the theoretical resolution threshold. Deep, narrow trenches and vias preferentially collect material at the damascene feature edges, leading to void formation. Electrochemical deposition (ECD) is currently the most widely used technique to fill trenches and vias with copper. However, ECD requires a seed layer. Chemical vapor depositions (CVD) and physical vapor depositions (PVD) are well-established Cu seed layer formation techniques.
Nonetheless, CVD and PVD do not inherently fill etched features preferentially over any other portion of substrate having nucleation sites. The preferential seeding of trenches with metal on which CVD or PVD deposited material can grow would yield selective deposition and lower the temperature of heating of the IC substrate during CVD or PVD to assure crystalline growth that degrades fine architecture structures on the substrate. Thus, the semiconductor industry is in need of an interconnect formation process capable of achieving higher resolution at lower temperature and ideally, at a lower cost.
The mesoscopic size regime between atoms and bulk materials is characterized by unusual properties. Mesoscopic systems exhibit collective atomic behavior, but not to a sufficient extent so as to preclude quantized effects. Many of the unusual thermodynamic and spectroscopic anomalies associated with mesoscopic systems are attributable to surface effects. Studies have shown surface energies that are 10 to 400% greater for nanocrystals than for bulk Au and Pt (C. Solliard and M. Flueli, Surf. Sci. 156, (1985), pp. 487-494) and Al (J. Wolterdorf, A. S. Nepijko and E. Pippel, Sur. Sci. 106, (1981), pp. 64-72). In the bulk, surface atoms represent such a small percentage of the total that surface effects are largely inconsequential. Surfaces generally possess modified atomic coordination numbers, geometries and diminished lattice energies relative to the bulk. The result of these modifications is that physical, spectroscopic, and thermodynamic properties, which are constant in the bulk, become size dependent variables in nanocrystals. Since a nanocrystal is a small portion of a bulk material lattice, nanocrystals are exploited in the present invention as seeds to produce thin film IC structures at low temperature.
Metallic nanocrystals have been shown to reduce melting temperatures compared with the bulk. (Ph. Buffat and J-P. Borel, Phys. Rev. A, 13, (1976), pp. 2287-2298. 2287-2298; C. J. Coombes, J. Phys., 2, (1972), pp. 441-449; J. Eckert, J. C. Holzer, C. C. Ahn, Z. Fu and W. L. Johnson, Nanostruct. Matls., 2, (1993). 407-413; C. R. M. Wronski, Brit. J. Appl. Phys. 18, (1967), pp. 1731-1737 and M. Wautelet, J. Phys. D, 24, (1991), 343-346). The depression in melting and annealing temperature is evident throughout the nanocrystal size regime, with the most dramatic effects observed in nanocrystals having a diameter from 2 to 6 nm. Melting studies on a range of nanocrystals have established that the melting temperature is size dependent in the nanometer size regime and is approximately proportional to the inverse particle radius regardless of the material identity. The size dependent melting temperature of metallic nanocrystals has included studies of Au, Pb and In, Al and Sn. (Au: Ph. Buffat and J-P. Borel, Phys. Rev. A, 13, (1976), 2287-2298. 2287-2298; Pb and In: C. J. Coombes, J. Phys., 2, (1972), 441-449; Al: J. Eckert, J. C. Holzer, C. C. Ahn, Z. Fu and W. L. Johnson, Nanostruct. Matls, 2, (1993), 407-413; and Sn: C. R. M. Wronski, Brit. J. Appl. Phys. 18, (1967), 1731-1737). The reduction in melting temperature as a function of nanocrystal size can be enormous. For example, 2 nm Au nanocrystals melt at about 300xc2x0 C., as compared to 1065xc2x0 C. for bulk gold. (M. Wautelet, J. Phys. D, 24, (1991), 343-346).
A method for producing a polycrystalline structure includes applying a metal in the form of nanocrystal seeds to a wafer having a trench or via cut therein. The nanocrystal seeds have a diameter between 2 and 40 nanometers. Thereafter, a substance is deposited onto the nanocrystalline seeds to form a polycrystalline structure. The presence of a nanocrystal seed functions herein as a nucleation site for crystal growth. A method for producing a microelectronic interconnect includes applying a solution comprising soluble copper nanocrystal seeds to a wafer having a trench or via cut therein have a diameter between 2 and 20 nanometers. Thereafter, copper is deposited onto the copper nanocrystal seeds to form a continuous polycrystalline copper interconnect within said trench or via.
A microelectronic structure is detailed including electrically isolated nanocrystalline domains. The domains are formed to an existing trench or via within a wafer substrate.
A method for healing a void in the film includes contacting a solution of nanocrystals dissolved in a solvent to the film and allowing the solvent to evaporate isolating the nanocrystals in the void. Thereafter, the nanocrystals are heated to fill the void with contiguous material derived from the nanocrystals wherein the void has irregular dimensions.
A method is detailed herein which uses a metal nanocrystal as a CVD or PVD seed to create interconnects or electrochemical deposition seed layers therefor by conventional processes. While the present invention is not limited to a particular metal, or metallic cation-containing compound such as an oxide, nitride, phosphide, or intermetallic, it is particularly well suited for the efficient formation of copper interconnects at temperatures below 400xc2x0 Celsius and even below 300xc2x0 Celsius. A silicon wafer that has been patterned by lithography and etched to form a series of trenches and/or vias is the substrate for the instant invention the exposed surface of which also contains SiO2. It is appreciated that an intermediate wetting layer is optionally applied to the substrate to promote interconnect wetting thereof and to prevent interdiffusion during subsequent IC processing.
A semiconductor processing method is provided for growing a polycrystalline metal film by preferably chemical vapor deposition (CVD) from a suitable precursor gas or gases on a substrate which has been coated with metal nanocrystal seeds, of the semiconductor material. The structure of the nanocrystal seeds serves as a template for the structure of the final polycrystalline film. The density of the seeds and the thickness of the grown polycrystalline film determine the grain size of the polycrystalline film at the surface of said film with more seeds, leading to small grain size. CVD onto the seeds to produce the polycrystalline film avoids the recrystallization step generally necessary for the formation of a polycrystalline film, and thus allows for the growth of polycrystalline films at reduced temperatures.
According to the present invention, polycrystalline metal film is grown on a substrate which has been previously coated with a film of metal seeds. There is no correlation between the structure of the substrate and the structure of the film. The film is preferably the result of an epitaxial CVD process on the surface of the nanocrystals, with the nanocrystal structure serving as a template for the crystal structure of said film. In addition, the density of nanocrystal seeds on the substrate surface control the final grain size of the grown polycrystalline film. The presence of the crystal seeds on the substrate also lowers the temperature for growth of a polycrystalline film. It is appreciated that a metal nanocrystal is also operative as a seed for PVD.
The nanocrystals are preferably made by a solution phase reduction from a metal salt as detailed in co-pending patent application Ser. No. 09/895,942. Other metal nanocrystal preparations are also operative including those detailed in H. Huang et al., Langmuir, 13 (1997) 172-175; I. Lisiecki and M. P. Pileni, J. Phys. Chem., 99 (14)(1995) 5077-5082; Nanoparticles and Nanostructured Films, J. H. Fendler, Wileyxe2x80x94VCH, 1998, Chapter 4. Alternative methods for metal nanocrystal synthesis include sputtering from a heated metal source within a vacuum chamber, as detailed in U.S. Pat. No. 5,830,538.
Upon coating a substrate with nanocrystal seeds, the substrate temperature is raised in the presence of an appropriate pressure of an appropriate gaseous organometallic to facilitate a thermal CVD process for growth onto the surface of the nanocrystal seeds or for PVD. The temperature of this process is substantially lower than would be required to grow a polycrystalline film on the substrate in the absence of the nanocrystal seeds.
A metal nanocrystal that has been solvent stabilized by a volatile surface passivating agent is applied to the substrate by a variety of conventional liquid deposition techniques illustratively including dip coating, spray coating, spin coating, and electrochemical deposition. As the nanocrystal solvent evaporates, metal nanocrystals are selectively stranded on the substrate. Preferably, the passivating agent is an organic molecule bonding to the metal through an oxygen, nitrogen or sulfur atom. The liquid chosen to volatilize and leave a bare metal nanocrystal surface having zero-oxidation state metal atoms thereon. Heating to a temperature of about 150xc2x0 C. to 250xc2x0 C. is sufficient to volatilize the passivating agent. Heating to 150xc2x0 C. to 250xc2x0 C. in order to volatilize the nanocrystal passivating agent is appreciated to often be sufficient to sinter the metal nanocrystal depending on nanocrystal domain size and the identity of the metal. Additional heating to a metal nanocrystal size-dependent melting temperature is optionally performed to provide a metal nucleation seed for CVD or PVD deposition that has thermodynamically reoriented relative to the substrate.
It is appreciated that metal salts also optionally serve as sources of metal nanocrystals by conventional liquid deposition techniques provided the salt is reduced by exposure to hydrogen gas or other reductant at a temperature below 400xc2x0 C. Optionally, a solution or dispersion of organometallics is applied by liquid deposition techniques. A particularly preferred organometallic is a metal hydrazine carboxylate that upon heating forms gaseous byproducts and a metal crystallite where the metal has a reduction potential of less than 0.9 eV.
The present invention identifies significant cost efficiencies based on the deposition characteristics of nanocrystal-based construction of electronic devices. The nanocrystal solutions or suspensions are applied by drip, spray or spin coating onto a trenched integrated circuit (IC) wafer. Unlike chemical and physical vapor deposition techniques, the present invention selectively deposits nanocrystal particulate in the IC trenches by taking advantage of the slower volatilization of a solvent carrier from trenches, causing the nanocrystals to congregate in high aspect ratio features. As a result, the quantity of extraneous deposition material, which must be removed by CMP, is diminished. Lastly, an environmental benefit results from pre-selecting aqueous and or benign organic solvents the nanocrystal solution, in place of solvents currently used in the chip manufacturing process.
Since evaporation of a solution of solubilizing metal nanocrystals or the sedimentation of solvent dispersed metal nanocrystals selectively isolates metal nanocrystals into trenched regions of a substrate, preferential to isolate on substrate plateaus subsequent CVD deposition occurs preferentially in substrate trenches. This aspect of the present invention affords trench or via selective CVD.
The inventive soluble metal nanocrystals are optionally applied to an existing metal layer in order to heal defects therein. Defect pores or voids in a metal layer formed by conventional techniques is preferably healed by evaporating a metal nanocrystal solution onto the defects thereby isolating the nanocrystals. With the nanocrystals able to penetrate any feature penetrable by solvent molecules, metal nanocrystals remain in such a feature upon solvent evaporation. The nanocrystals are applied to a metal layer formed by CVD, PVD or ECD. A solubilized metal nanocrystal optionally includes ligands imparting mobility to the nanocrystal in an electric field thereby allowing a nanocrystal to migrate in an electric field. As such, the inventive soluble nanocrystals are operative as an additive to an electrochemical deposition bath.
In electrochemical baths, a metal nanocrystal surface is derivatized with a passivating liquid making the nanocrystal soluble in aqueous, alcoholic or other organic solvent. Such a solution is operative as an electrophoretic deposition bath where the substrate functions as an electrode of the attractive polarity relative to the nanocrystal with a polar ligand terminus imparting polar solvent solubility and a change per unit area of nanocrystal surface.
The present invention also identifies cost savings associated with production defects. Nanocrystal deposition of interconnects is both reversible and repairable. Poor deposition technique is corrected by resolubilizing nanocrystals stranded on a trenched IC substrate by solvent washing prior to sintering the nanocrystals. Further, trench regions showing incomplete filling or separation from the trench walls can be remedied after sintering or melting to form bulk material interconnect features through the reapplication of a nanocrystal solution. Because the solvent containing the nanocrystals can freely penetrate fissures and voids associated with an IC patterned for an interconnect, additional nanocrystals are deposited into poorly filled regions.
A nanocrystal solution is applied to flood the wafer surface. The solvent penetrates the trench recesses within the wafer surface, including those shadowed or otherwise obscured from evaporative methods. In the process nanocrystals dissolved or suspended in the solution are carried into these regions. The solvent volatilizes more quickly from the wafer plateaus as compared to the recesses causing the nanocrystals to become concentrated in the shrinking solvent pools within the recesses. The nanocrystals become stranded in the drying trenches. Heating the wafer to a temperature sufficient to sinter or melt contiguous nanocrystals results in the formation of bulk polycrystalline domains.
In the case of many technologically important interconnect materials such as copper, the intermediate layer is illustratively a layer of TiN or TaN having a sufficient thickness to assure continuity. Other such intermediate layers are formed by evaporation of a base metal layer onto the trenched substrate and thereafter exposing the base metal layer to a nitrogen plasma to induce a surface nitriding as is conventional to the art.
A solution of dissolved or suspended nanocrystals is applied to the contoured surface of the wafer. Preferably, the nanocrystal solution or suspension is concentrated to facilitate a desired metal nanocrystal seed density on the substrate.
The solvent utilized to form the solution is optionally aqueous or organic. The solvent is chosen based on factors including, but not limited to hydrophilicity of the wafer surface, solubility of the nanocrystals therein, vapor pressure, toxicity, purity and the like.
The nanocrystal is defined as a particle having a linear dimension in any direction on the order of nanometers, namely 1 to 100 nm in diameter. Preferably, the nanocrystal of the present invention is between 2 and 20 nm. More preferably, the nanocrystal of the present invention is between 2 and 10 nm. The size distribution of the nanocrystals in solution is of some importance, since the sintering temperature of particles in this size regime is size dependent. Likewise, the melting temperature is size dependent. Preferably, a size distribution of less than 30% of the average particle diameter is used for nanocrystals of an average diameter of less than about 6 nm with increasingly greater tolerances being preferred as the average particle increases beyond 6 nm. The nanocrystals are optionally either dispersed in a solvent by conventional means illustratively including sonication, agitation, solution shearing and the like; or the nanocrystal surface is coupled to a passivating agent by adsorption or chemically bonding thereto. The passivating agent preferably being soluble in the solvent and thus imparting solubility to the particles. Preferably, the nanocrystals are soluble to promote segregation into low volatilization rate, trench and via regions, as compared to wafer plateaus. More preferably, the nanocrystals are copper for the formation of an interconnect.
The passivating agent is introduced to prevent nanocrystal growth beyond a pre-selected size and preferably to also impart solubility on the nanocrystal in a solvent. The passivating agent illustratively includes a variety of thermally volatile organics including those of the formula XRY where X is a moiety capable of chemically bonding to a surface atom of the nanocrystal and illustratively includes alcohol, amine, carboxylate, ketone, thiol, imide, amide, sulfonyl, nitryl, aldehyde, and phosphorus containing moeities; R is C1-C30 aliphatic, aryl or heteroatom substituted derivative thereof and Y is X or hydrogen. The RY portion of the passivating agent is optionally chosen to interact with the solvent to impart solubility. In another embodiment, Y bonds to the surface of a second nanocrystal to tether nanocrystals together. Further, dendritic or polymeric variants of XRY are operative to form an extended matrix of nanocrystals. Preferably, the passivating agent is a linear C2-C24 alkane-thiol, -amine, -carboxylate, nitrogen- or phosphorus-containing moiety. The nanocrystal surface binding passivating agent moiety being dictated by established organometallic chemistry.
Nanocrystals are applied to the wafer by applying the solution thereto. Layering a solution of the instant invention onto a wafer is operative. Preferably, the solution is applied in such a way as to promote uniform deposition of the nanocrystals across whole wafers, such methods illustratively include atomizing the solution and applying as a fine nanocrystal paint spray; and spin coating the solution onto a rotating wafer. Optionally, a binder is dispersed in the solution to minimize particle movement as the solvent pool evaporates. A binder useful in the present invention includes low molecular weight and polymeric organic substances. The binder being chosen such that upon heating to a temperature of less than about 250 to 300xc2x0 Celsius, the binder is volatilized. The binder is chosen to minimize binder residues, the residues likely to decrease conductivity of the bulk domain resulting from heating the nanocrystals. Binders illustratively include waxes; aliphatic compounds containing at least eight carbon atoms including carboxylic acids alcohols, aldehydes, amines, thiols and salt thereof wherein the cation is a conductive metal ion illustratively including copper aluminum, magnesium, gold, silver, manganese, molybdenum and the like; polymeric materials which volatilize to greater than 95% by weight below 250xc2x0 Celsius including poly (acrylic acid), polyglycols, polycarbonates, polyalkyls, polyalcohols, polyesters and the like; proteinaceans substrates such as albumin, gelatin and collagen; carbohydrates; and organosilanes.
The nanocrystal seeds of the instant invention are composed of any material that is conventionally used to create interconnect structures, intermediate layers or barrier structures in microelectronics. These materials illustratively include: aluminum, copper, gold, manganese, molybdenum, nickel, palladium, platinum, tin, zinc, tantalum, titanium and silver, alloys, oxides, nitrides and phosphides thereof. Further, in instances where one wishes to create a metal-oxide-semiconductor (MOS) junction intermediate or barrier structures, nanocrystals of the metallic elements may be deposited and oxidized to positive oxidation state greater than zero by heating to a temperature of less than 500xc2x0 Celsius or subjecting the metal to a gaseous plasma in an atmosphere of the gaseous oxidant. The metallic elements being oxidized to form a variety of metal compounds including oxides, nitrides, and phosphides. Alternately, nanocrystals of the oxides are synthesized and stranded directly into IC wafer trenches and vias to serve as deposition seeds. It is appreciated that upon heating metallic nanocrystals in order to form conductive structures, it may be necessary to perform such heating under an inert or reducing atmosphere to prevent unwanted oxidation.
There are several temperature ranges important to the process of an operative IC structure using nanocrystal seeds. In a preferred embodiment, the nanocrystal surface is coated with a passivating agent that imparts solvent solubility to the nanocrystal. Upon heating a nanocrystal coated wafer above the passivating agent thermalization temperature, the passivating agent is volatilized allowing clean nanocrystal surfaces of contiguous nanocrystals into contact and to act as deposition seeds. While the passivating agent volatilization temperature is largely size independent and related to the chemisorption or physisorption energy between the passivating agent and the nanocrystal surface atoms, nanocrystal sintering and melting temperature are controllable over hundreds of degrees Celsius through nanocrystal size domain selection. The PVD or CVD temperature onto nanocrystal seeds is lower than the same process absent the inventive seeds, preferably, greater than 50xc2x0 C. less than the process absent salt seeds.
It is appreciated that the inventive process is operative with supercritical fluid deposition, such as supercritical deposition of copper of material, where the nanocrystal seeds promote trench selective deposition although not necessarily at a different process temperature. Sintering is defined as the interfacial coalescence of contiguous particles while the particle cores retain prior crystalline properties. Sintering temperature is calculable or approximated as two-thirds of the substance melting temperature in degrees Kelvin. Further, heating beyond the sintering temperature brings the nanocrystals to a size dependent melting temperature. Melting of a contiguous matrix of nanocrystals results in a densified polycrystalline bulk structure.
The present invention is capable of overcoming prior art limitations regarding dimensional shrinkage associated with densification, thin film instability through repetitive nanocrystal solution application. (K. T. Miller et al. J. Mater Res. 5 (1990) 151-160; B. A. Korgel and D. Fitzmaurice Phys. Rev. Let 80 (1998) 3531-3534; A. G. Evans et al. J. Mater Res. 3 (1988) 1043-1049).
Significant shrinkage is associated with passivating agent volatilization, thus after applying a nanocrystal solution to a wafer, the wafer is heated to the passivating agent volatilization temperature and additional nanocrystal solution optionally are applied to fill feature voids associated with volatilization. This process is optionally repeated prior to raising the wafer to a sintering of melting temperature for the nanocrystal mass filling a wafer trench or via. It is appreciated that nanocrystal deposition is optionally carried out at a temperature above the passivating agent volatilization temperature such that active nanocrystal surfaces are formed upon contact with a trenched wafer.
The relevant volatilization, sintering, and melting temperatures for a given nanocrystal solution are determinable through thermal analysis, techniques such as differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), temperature dependent spectroscopies and conductivity.
In instances where the interconnect is being deposited onto a silicon oxide surface other factors need to be considered. Metals often poorly wet oxide surfaces and thus an intermediate conventional adhesion-promoting layer is applied. In those instances where a hydrophobic solvent is used to coat a hydrophilic oxide surface, the solvent can be induced to wet the oxide surface by washing the wafer surface with a silanol or similar surfactant prior to deposition of the particle containing solvent. The silanol wash creates a thin layer that projects organic functionalities away from the surface which attractively interact with the particle surfaces of hydrophobic particles and simultaneously bonds to the oxide surface through the hydroxyl functionality. It is appreciated that other adhesion promoters known to the art of laminating non-wettable oxide and metallic layers are operative herein under the disclosed thermal conditions.
Having described the inventions, the following illustrative examples are provided which are not intended to limit the scope of the invention.